CN109908933B

CN109908933B - Ozone catalytic oxidation catalyst and preparation method thereof

Info

Publication number: CN109908933B
Application number: CN201711325674.9A
Authority: CN
Inventors: 赵越; 蒋广安; 李宝忠; 马传军; 王雪清
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2017-12-13
Filing date: 2017-12-13
Publication date: 2021-11-09
Anticipated expiration: 2037-12-13
Also published as: CN109908933A

Abstract

The invention discloses an ozone catalytic oxidation catalyst and a preparation method thereof, wherein the catalyst comprises a composite carrier and an active metal component, transition metal is used as the active metal component, and the composite carrier comprises active carbon and basic carbonate. The preparation method comprises the steps of mixing activated carbon and a soluble organic salt solution, introducing a carbonate solution or an alkaline solution into a material A after uniformly mixing, and obtaining a material B, and carrying out solid-liquid separation, drying and roasting to obtain a material C; and mixing the material C with water, introducing carbon dioxide gas for reaction, cooling, performing solid-liquid separation, drying and roasting a solid phase obtained by separation to obtain a composite carrier material, finally impregnating active metal and optional auxiliary agent components, and drying and roasting to obtain the catalyst. The catalyst has the advantages of simple preparation process, good stability, high COD removal capacity and capability of relieving the problem of metal loss.

Description

Ozone catalytic oxidation catalyst and preparation method thereof

Technical Field

The invention relates to a catalytic material and a preparation method thereof, in particular to an ozone catalytic oxidation catalyst and a preparation method thereof.

Background

As water resources are increasingly scarce, the national control on the total emission amount of pollutants in water is increasingly strict, the formulation of new standards provides new challenges for the prevention and treatment work of water pollution in China, and most discharged wastewater cannot meet the emission requirements of the new standards. Therefore, the external sewage needs to be deeply treated to achieve standard discharge and even can be recycled, which is of great significance in reducing the discharge amount of discharged pollutants of the wastewater, reducing the pollution discharge cost of enterprises, reducing the consumption of water resources and the like.

Nondegradable organic sewage at home and abroadMuch research has been carried out on the treatment of dyeing wastewater, and advanced oxidation technology (AOP) has emerged in the past two decades with its great potential and unique advantages. Compared with other traditional water treatment methods, the AOP technology is a free radical chain reaction, has the advantages of short reaction time, high reaction speed, controllable process, no selectivity and the like, can completely degrade various organic pollutants, and does not generate secondary pollution. Hydrogen peroxide and ozone are commonly used AOP oxidants. The hydrogen peroxide generates hydroxyl radicals by a Fenton method, but the used homogeneous catalyst has the problems of more used medicaments, difficult recovery and the like, and is easy to cause secondary pollution. The ozone oxidation treatment of wastewater is an advanced oxidation technology, but the ozone single oxidation technology is limited by the defects of high selectivity of organic matters, incapability of thoroughly oxidizing the organic matters and the like, and is difficult to achieve the best treatment effect. The catalytic oxidation of ozone can convert ozone in water solution into hydroxyl radical (OH) with higher oxidation potential by the action of catalyst, and the OH reacts with most organic matters almost without selectivity and the reaction rate is 10⁶～10¹⁰ M^-1•s^-1And the reaction rate is about 7 orders of magnitude higher than that of ozone and organic matters. The organic matters which are difficult to be oxidized or degraded by ozone alone can be oxidized at normal temperature and normal pressure so as to purify the water quality. The catalytic ozonation can overcome the defect of single ozonation, thereby becoming a novel advanced oxidation technology with more practical value.

The key point of the ozone catalytic oxidation technology is the development of a catalyst, the used catalyst is divided into a homogeneous phase catalyst and a heterogeneous phase catalyst, and similar to a Fenton method, the homogeneous catalyst has the problems of difficult recovery and easy secondary pollution, so the research is mostly concentrated on the heterogeneous catalyst.

The heterogeneous solid catalyst is mainly a catalyst which is formed by taking active carbon, molecular sieve, amorphous alumina, titanium dioxide and the like as carriers and taking one or more of alkali metal, alkaline earth metal, transition metal or Pt and Pd noble metal as active components. The active carbon is a kind of microcrystal carbon which is made of carbon-containing substance and has the advantages of black color, developed pores, large specific surface area and strong adsorption capacity. The activated carbon has stable property, is acid-resistant, alkali-resistant and heat-resistant, is insoluble in water or organic solvent, is easy to regenerate, is an environment-friendly adsorbent, and is widely applied to the fields of treatment of industrial three wastes, food, medicine, carriers, semiconductors, batteries, electric energy storage and the like. At present, activated carbon is mostly selected as a carrier for a multiphase solid catalyst for wastewater treatment, but the catalyst prepared by selecting activated carbon loaded metal has poor wear resistance and low mechanical strength, and the loaded metal is easy to run off, so that the application effect of the activated carbon catalyst is reduced.

CN200610089575.0 discloses an activated carbon-supported copper oxide catalyst and a preparation method thereof, wherein the preparation method of the catalyst comprises the following steps: soaking the activated carbon in 10% NaOH solution for 24h, filtering, and washing with deionized water to neutrality; then 10% HNO is used₃Soaking the solution for 24 hours, filtering, washing the solution to be neutral by deionized water, putting the solution into a drying oven, and drying the solution at 100-110 ℃; adding 0.2 to 0.3mol/L of Cu (NO)₃)₂Adding the treated active carbon into the solution, fully stirring, and dropwise adding 20% NaHCO₃And (3) until a large amount of precipitate is generated, curing for 24h, filtering, washing with deionized water until no metal ions are separated out, drying in an oven at 100-110 ℃ to obtain an activated carbon-supported copper oxide solid, and activating at 270-280 ℃ for 2.5h to obtain the activated carbon-supported copper oxide catalyst.

CN201210323265.6 discloses an activated carbon/alumina composite catalyst carrier and a preparation method thereof, and the activated carbon/alumina composite catalyst carrier is prepared by mixing acid-washed activated carbon with gamma-alumina, adding a composite auxiliary agent, kneading, extruding and roasting in nitrogen atmosphere. The material is still a physical mixture of alumina and activated carbon, the alumina and the activated carbon are not uniformly dispersed, and the comprehensive performance of the material needs to be further improved.

CN201510298192.3 discloses a method and equipment for preparing a surface vitrified carbon adsorption material, which comprises the steps of firstly mixing activated carbon powder and a binder to form activated carbon core particles, then taking the activated carbon core particles as mother spheres, uniformly adhering a vitrified material on the outer surfaces of the activated carbon core particles, drying, preheating at a medium temperature, sintering at a high temperature, and discharging at room temperature to obtain the activated carbon particles with vitrified surfaces. The active carbon in the particles prepared in this way cannot be directly contacted with the wastewater, and the catalytic performance of the particles is weakened.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides an ozone catalytic oxidation catalyst and a preparation method thereof.

The invention provides an ozone catalytic oxidation catalyst, which comprises a composite carrier and an active metal component, wherein one or more of transition metals Fe, Cu, Mn, Ti and Zn are used as the active metal component, the composite carrier comprises active carbon and basic carbonate, and the basic carbonate is distributed on the outer surface of the active carbon, wherein the active carbon accounts for 35-90% of the total weight of the composite carrier, and preferably 40-80%; the basic carbonate accounts for 10-65% of the total weight of the composite carrier, and preferably 20-60%; the basic carbonate is basic magnesium carbonate or a mixture of the basic calcium carbonate and the basic magnesium carbonate.

The active metal component in the invention is one or more of transition metals Fe, Cu, Mn, Ti and Zn, and the transition metal accounts for 0.1-20.0% of the total mass of the catalyst in terms of oxidation.

The catalyst also comprises an auxiliary agent component, wherein the auxiliary agent component is rare earth metal, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium; the rare earth metal accounts for 0.1 to 15.0 percent of the total mass of the catalyst by oxide.

The active carbon used in the invention is powdery active carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m²A pore volume of 0.5-1.8 cm³(ii)/g, the average pore diameter is 0.5 to 4.0nm, and the pore volume of pores having a pore diameter of 1 to 2nm accounts for 90% or more of the total pore volume.

The active carbon in the invention can be selected from conventional powdery active carbon commodities, such as various wood active carbon, shell active carbon and coal-based active carbon; or can be selected from various activated carbon products obtained by conventional preparation methods of wood materials, mineral materials, plastics and wastes, such as wood, sawdust, charcoal, coconut shells, fruit pits, fruit shells, coal carbon, coal gangue, petroleum coke, petroleum pitch, polyvinyl chloride, polypropylene, organic resin, waste tires, residual sludge and the like.

The properties of the composite carrier of the invention are as follows: the specific surface area is 150-1500 m²A pore volume of 0.1 to 1.2 cm/g³(ii)/g, the average pore diameter is 1-8 nm.

In the catalyst of the present invention, the properties of the catalyst are as follows: the specific surface area is 120-1200 m²A pore volume of 0.1 to 1.8 cm/g³G, abrasion Rate<3wt% and a side pressure strength of 80 to 250N/cm.

When the basic carbonate is a mixture of basic calcium carbonate and basic magnesium carbonate, the basic calcium carbonate and the basic magnesium carbonate can be mixed in any proportion.

The second aspect of the present invention provides a method for preparing an ozone catalytic oxidation catalyst, comprising the following steps:

(1) mixing activated carbon and a soluble organic salt solution uniformly to obtain a material A, wherein the soluble organic salt solution is a soluble organic magnesium salt solution or a mixed solution of a soluble organic calcium salt solution and a soluble organic magnesium salt solution;

(2) introducing a carbonate solution or an alkaline solution into the material A obtained in the step (1), uniformly mixing, and standing to obtain a material B;

(3) performing solid-liquid separation on the material B obtained in the step (2), and drying and roasting a solid phase obtained by separation to obtain a material C;

(4) mixing the material C obtained in the step (3) with water, introducing carbon dioxide gas for reaction, cooling, performing solid-liquid separation, and drying and roasting a solid phase obtained by separation to obtain a composite carrier;

(5) and (4) impregnating active metal and optional auxiliary agent components on the composite carrier material obtained in the step (4), and then drying and roasting to obtain the catalyst.

In the preparation method, the activated carbon used in the step (1) is powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m²A pore volume of 0.5-1.8 cm³(ii)/g, the average pore diameter is 0.5 to 4.0nm, and the pore volume of pores having a pore diameter of 1 to 2nm accounts for 90% or more of the total pore volume. The above-mentionedThe activated carbon can be selected from conventional powdered activated carbon commodities, such as various wood activated carbons, shell activated carbons and coal-based activated carbons; or can be selected from various activated carbon products obtained by conventional preparation methods of wood materials, mineral materials, plastics and wastes, such as wood, sawdust, charcoal, coconut shells, fruit pits, fruit shells, coal carbon, coal gangue, petroleum coke, petroleum pitch, polyvinyl chloride, polypropylene, organic resin, waste tires, residual sludge and the like.

In the preparation method of the invention, the soluble organic calcium salt in the step (1) is one or more of calcium gluconate, calcium acetate, calcium lactate, calcium amino acid, calcium L-aspartate and calcium L-threonate, and preferably adopts calcium gluconate or calcium lactate.

In the preparation method of the invention, the soluble organic magnesium salt in the step (1) is one or more of magnesium gluconate, magnesium acetate, magnesium lactate, magnesium amino acid, magnesium L-aspartate and magnesium L-threonate, and preferably magnesium gluconate or magnesium lactate is adopted.

In the preparation method, the activated carbon and the soluble organic salt in the step (1) are mixed according to the ratio of C: m²⁺The molar ratio is 4.3-84.7: 1, and the ratio of C: m²⁺The molar ratio is 10-60: 1, wherein M represents Mg or Ca and Mg.

In the preparation method, the carbonate in the step (2) is one or more of ammonium carbonate, potassium carbonate and sodium carbonate, and preferably ammonium carbonate; the concentration of the carbonate solution is 0.1-1.0 mol/L.

In the preparation method of the invention, the carbonate dosage in the step (2) is CO₃ ^2-：M²⁺The molar ratio is 1-1.2: 1, and CO is preferably selected₃ ^2-：M²⁺The molar ratio is 1: 1.

In the preparation method of the invention, the alkaline solution in the step (2) is an inorganic alkaline solution, and specifically can be ammonia water, sodium hydroxide or potassium hydroxide.

In the preparation method, an alkaline solution is introduced into the material A obtained in the step (1) in the step (2), and then the pH value is adjusted to 8-9.

The preparation method of the inventionIn the method, the dosage of the alkaline solution in the step (2) is OH^-：M²⁺The molar ratio is 2-4: 1, and OH is preferred^-：M²⁺The molar ratio is 2-2.5: 1, wherein M represents Mg or Ca and Mg.

In the preparation method, the drying temperature in the step (3) is 70-110 ℃, preferably 80-100 ℃, and the drying time is 2-6 hours, preferably 3-4 hours.

In the preparation method, the roasting in the step (3) is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere is one of argon and helium. In the step (3), the roasting temperature is 500-1200 ℃, preferably 600-900 ℃, and the roasting time is 2-8 hours, preferably 3-5 hours.

In the preparation method, the material C in the step (4) is mixed with water at the temperature of 60-100 ℃.

In the preparation method, the partial pressure of the carbon dioxide in the step (4) is 0.08-1.0 MPa.

In the preparation method, the reaction end point pH in the step (4) is 7.0-10.0, preferably 8.0-9.0.

In the preparation method, the reaction temperature in the step (4) is 15-150 ℃.

In the preparation method, the drying temperature in the step (4) is 40-100 ℃, preferably 40-60 ℃, and the drying time is 3-24 hours, preferably 6-8 hours.

In the preparation method, the roasting in the step (4) is carried out in nitrogen or inert atmosphere, and the inert atmosphere is one of argon and helium. In the step (4), the roasting temperature is 80-220 ℃, the roasting time is 2-6 h, and the roasting time is preferably 3-4 h, wherein the roasting time is preferably 150-200 ℃.

In the preparation method of the present invention, the solid-liquid separation in steps (3) and (4) may adopt any scheme capable of realizing solid-liquid separation in the field, such as solid-liquid separation by filtration, etc.

In the preparation method of the invention, when the active metal component and the optional auxiliary component are impregnated on the composite carrier material obtained in the step (4) in the step (5), the composite carrier material obtained in the step (4) is preferably prepared and molded firstly, and then the active metal component and the optional auxiliary component are impregnated on the composite carrier material, the molding technology of the composite carrier adopts any technology which can realize molding in the prior art, and the shape of the molded carrier is any one of a cylinder shape, a hollow cylinder shape, a clover shape and a spherical shape.

In the preparation method, the active metal component in the step (5) is one or more of transition metals Fe, Cu, Mn, Ti and Zn, and the transition metals account for 0.1-20.0% of the total mass of the catalyst in terms of oxides.

In the preparation method, the auxiliary agent component in the step (5) is rare earth metal, and the rare earth metal oxide accounts for 0.1-15.0% of the total mass of the catalyst. The rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium.

In the preparation method of the invention, the carrier impregnation active metal and the auxiliary agent component in the step (5) can be spray impregnation, saturated impregnation or supersaturated impregnation. When in impregnation, the impregnation sequence of the active metal and the auxiliary agent has no special requirements.

In the preparation method, after the catalyst in the step (5) is impregnated, the catalyst is dried for 1-15 hours under the drying condition of 40-100 ℃, the roasting temperature is 100-220 ℃, and the roasting time is 1-10 hours. The calcination is carried out in a nitrogen or inert atmosphere.

In the method of the present invention, the mixing may be performed by any of stirring, shearing, ultrasonic treatment, and the like.

Compared with the prior art, the invention provides an ozone catalytic oxidation catalyst and a preparation method thereof, the catalyst adopts a novel composite carrier and the preparation method, basic magnesium carbonate or basic calcium carbonate and basic magnesium carbonate is introduced into the outer surface of active carbon in the composite carrier, and compared with a pure active carbon carrier, the relative content of the active carbon in the carrier is reduced, so that the utilization rate of free radicals can be improved, and the problems that the generation of hydroxyl free radicals is accelerated, the collision probability between free radicals is increased and the concentration of the free radicals is weakened due to overhigh content of the active carbon in the existing pure active carbon catalyst are solved. Hydroxyl contained in the basic calcium carbonate and the basic magnesium carbonate is introduced into the outer surface of the composite carrier, so that the decomposition of ozone is promoted to generate hydroxyl radicals, a free radical chain reaction is further initiated, and the utilization efficiency of the hydroxyl radicals can be improved to the maximum degree by controlling the content of the hydroxyl radicals by adjusting the content of the basic magnesium carbonate or the basic calcium carbonate and the basic magnesium carbonate. When the active metal supported active carbon composite carrier is used for wastewater treatment, the basic calcium carbonate and the basic magnesium carbonate can adsorb active metal ions dissolved out from the catalyst, so that secondary pollution caused by the active metal ions is avoided.

In the preparation of the catalyst composite carrier, the macromolecular organic magnesium salt or the macromolecular organic calcium salt and macromolecular organic magnesium salt solution is mixed with the active carbon, and molecules of the macromolecular organic calcium salt and the macromolecular organic magnesium salt are difficult to enter into the pore channels of the active carbon, so that calcium ions and magnesium ions are almost completely attached to the surface of the active carbon, the organic calcium salt and the organic magnesium salt solution are prevented from entering into the pore channels of the active carbon, and the generated basic calcium carbonate and basic magnesium carbonate can be prevented from blocking the pore channels and influencing the performance of the carrier. The preparation process of the composite carrier is an in-situ generation process of organic calcium salt/organic magnesium salt-calcium carbonate/magnesium (calcium hydroxide/magnesium) -basic calcium carbonate/magnesium, the basic calcium carbonate/magnesium is firmly attached to the outer surface of the active carbon, the mechanical mixing of the active carbon and the basic calcium carbonate/magnesium is more uniform and firm, and the defect that pore channels are blocked due to in-situ generation in pores is avoided. Meanwhile, organic components in the organic calcium/magnesium salt can generate part of carbon in the roasting stage, the part of carbon can play a role of an adhesive, and the generated calcium/magnesium salt is organically connected with the original activated carbon carrier, so that the firmness between the basic calcium/magnesium carbonate and the activated carbon in the composite carrier is improved, the strength of the formed carrier is enhanced, and the abrasion is reduced.

Detailed Description

The preparation process of the present invention is further illustrated below with reference to specific examples, but the scope of the present invention is not limited to these examples.

The specific surface area and the pore volume of the product are measured by adopting a low-temperature liquid nitrogen physical adsorption method.

The specific surface area of the commercially available activated carbon used in the present invention was 828m²G, pore volume 0.8cm³The average pore radius is 2.1nm, the iodine adsorption value is 700mg/g, and the granularity is 200 meshes.

Example 1

Adding 50g of activated carbon powder into 200g of magnesium gluconate solution with the mass fraction of 18%, slowly stirring, and soaking for 4 hours; slowly adding 290mL of 0.6mol/L sodium hydroxide solution dropwise under stirring to generate magnesium hydroxide precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1100 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide compound. Adding the obtained compound into 200g of distilled water with the temperature of 90 ℃, introducing CO after 2h₂And (3) controlling the end point pH to be 7.5 under the conditions of gas pressure of 0.18MPa and temperature of 150 ℃, naturally cooling, filtering, drying at 70 ℃ for 8 hours, and roasting at 180 ℃ for 4 hours under the protection of nitrogen to obtain the active carbon and basic magnesium carbonate composite carrier material. The obtained carrier material is made into a spherical shape with the diameter of 3mm, dried at the temperature of 80 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. According to its water absorption rate, Ti (SO)₄)₂·9H₂O and Pr (NO)₃)₃·6H₂Oin TiO₂And Pr₂O₃Respectively accounting for 10.0 percent and 0.5 percent of the total weight of the catalyst to prepare solutions. And (3) spraying and soaking the Ti-Pr solution in the carrier ball in the same volume in a shot blasting machine, standing for 2 hours, drying at 80 ℃, roasting for 4 hours at 170 ℃ under the protection of nitrogen, cooling to room temperature, and taking out to obtain the catalyst A1. The properties of the catalyst are shown in table 1.

Example 2

Adding 50g of activated carbon powder into 250g of L magnesium lactate solution with the mass fraction of 19.2%, slowly stirring, and soaking for 4 hours; slowly adding 270mL of ammonium carbonate solution with the concentration of 0.7mol/L dropwise under stirring to generate magnesium carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1100 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide compound. Adding the obtained compound into 200g of distilled water with the temperature of 85 ℃, introducing CO after 2h₂Gas, the pressure is 0.36MPa,controlling the end point pH to be 8.0 at the temperature of 90 ℃, naturally cooling, filtering, drying at 70 ℃ for 8h, and roasting at 200 ℃ for 2h under the protection of argon to obtain the active carbon and basic magnesium carbonate composite carrier material. The obtained carrier material is made into clover shape with the diameter of 2.5mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. With Zn (NO)₃)₂·6H₂O and Ce (NO)₃)₃·6H₂O as ZnO and CeO₂The catalyst is prepared into 1000 mL solution according to the proportion of 2.0 percent and 10.5 percent of the total weight of the catalyst respectively. And (3) supersaturating and impregnating the carrier strip with a Zn-Ce solution, stirring for 3 hours at 60 ℃ in a constant-temperature water bath, standing for 24 hours in the air, then evaporating to dryness in vacuum at 80 ℃ by using a rotary evaporator, and drying the obtained sample in a drying box at 100 ℃. Then roasting the mixture for 6 hours at 150 ℃ under the protection of nitrogen, and taking out the mixture after the temperature is reduced to room temperature to obtain the catalyst A2. The properties of the catalyst are shown in table 1.

Example 3

Adding 100g of activated carbon powder into 300g of a magnesium L-aspartate solution with the mass fraction of 10%, slowly stirring, and soaking for 4 hours; slowly dripping 210mL of ammonia water with the concentration of 1.0mol/L under stirring to generate magnesium carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1100 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide compound. Adding the obtained compound into 200g of distilled water with the temperature of 90 ℃, introducing CO after 1h₂And (3) controlling the end point pH to be 9.0 at the temperature of 110 ℃ under the pressure of 0.15MPa, naturally cooling, filtering, drying at 70 ℃ for 8h, and roasting at 200 ℃ for 2h under the protection of argon to obtain the activated carbon and basic magnesium carbonate composite carrier material. The obtained carrier material is prepared into clover shape with the grain diameter of 2.5mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. With Mn (NO)₃)₂·4H₂O and La (NO)₃)₃·6H₂Oto MnO₂And La₂O₃1000 mL of solution was prepared in proportions of 1.5% and 8.5% of the total weight of the catalyst, respectively. And (3) supersaturating and dipping the carrier strip by using a Mn-La solution, stirring for 3 hours at 60 ℃ in a constant-temperature water bath, standing for 24 hours in the air, then evaporating to dryness in vacuum at 80 ℃ by using a rotary evaporator, and drying the obtained sample in a drying box at 100 ℃. Then under the protection of nitrogenRoasting at 150 deg.c for 6 hr, cooling to room temperature and taking out to obtain catalyst A3. The properties of the catalyst are shown in table 1.

Example 4

Adding 100g of activated carbon powder into 300g of mixed solution of magnesium gluconate with the mass fraction of 8.5% and calcium gluconate with the mass fraction of 7.2%, slowly stirring, and soaking for 4 hours; slowly adding 225mL of ammonium carbonate solution with the concentration of 0.5mol/L dropwise under stirring to generate carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1000 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide-calcium oxide compound. Adding the obtained compound into 200g of distilled water with the temperature of 80 ℃, introducing CO after 2h₂And (3) controlling the end point pH to be 8.2 under the conditions of gas pressure of 0.22MPa and temperature of 120 ℃, naturally cooling, filtering, drying at 70 ℃ for 3h, and roasting at 180 ℃ for 2h under the protection of nitrogen to obtain the active carbon, basic magnesium carbonate and basic calcium carbonate composite carrier material. The obtained carrier material is made into a clover shape with the diameter of 1.7mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst forming carrier. With Cu (NO)₃)₂·3H₂O and La (NO)₃)₃·6H₂O as CuO and La₂O₃Respectively accounting for 5.0 percent and 1.0 percent of the total weight of the catalyst to prepare 1000 mL of solution. And supersaturating and dipping the carrier strip by using a Cu-La solution, stirring for 3 hours at 60 ℃ in a constant-temperature water bath, standing for 24 hours in air, then evaporating to dryness in vacuum at 80 ℃ by using a rotary evaporator, and drying the obtained sample in a drying box at 100 ℃. Then roasting the mixture for 4 hours at 200 ℃ under the protection of nitrogen, and taking out the mixture after the temperature is reduced to room temperature to obtain the catalyst A4. The properties of the catalyst are shown in table 1.

Example 5

Adding 100g of activated carbon powder into 300g of mixed solution of 14.6 percent of magnesium gluconate and 5.1 percent of L-calcium lactate in mass fraction, slowly stirring and soaking for 4 hours; slowly dropwise adding 200mL of 0.8mol/L sodium carbonate solution under stirring to generate carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1100 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide-calcium oxide compound. The resulting complex was added to 200g of a distillation at 90 deg.CIntroducing CO into water after 1h₂And (3) controlling the end point pH to be 7.7 under the conditions of gas pressure of 0.30MPa and temperature of 140 ℃, naturally cooling, filtering, drying at 50 ℃ for 6 hours, and roasting at 140 ℃ for 4 hours under the protection of nitrogen to obtain the activated carbon, basic magnesium carbonate and basic calcium carbonate composite carrier material. The obtained carrier material is made into clover shape with the diameter of 2.5mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. According to its water absorption rate, Fe (NO)₃)₃·9H₂O and Ce (NO)₃)₃·6H₂O is Fe₂O₃And CeO₂The catalyst is prepared into solution respectively accounting for 5.0 percent and 1.5 percent of the total weight of the catalyst. Soaking the carrier strip with Fe-Ce solution in the same volume for 2 hours, drying at 80 ℃, roasting at 180 ℃ for 6 hours in nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst A5. The properties of the catalyst are shown in table 1.

Example 6

Adding 50g of activated carbon powder into 300g of mixed solution of 12.8 percent of magnesium L-aspartate and 6.3 percent of calcium acetate respectively, slowly stirring and soaking for 4 hours; slowly dropwise adding 570mL of potassium hydroxide solution with the concentration of 0.9mol/L under stirring to generate hydroxide precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1100 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide-calcium oxide compound. Adding the obtained compound into 200g of distilled water with the temperature of 85 ℃, introducing CO after 2h₂And (3) controlling the end point pH to be 8.5 under the conditions of gas pressure of 0.26MPa and temperature of 120 ℃, naturally cooling, filtering, drying at 70 ℃ for 4h, and roasting at 160 ℃ for 3h under the protection of nitrogen to obtain the activated carbon, basic magnesium carbonate and basic calcium carbonate composite carrier material. The obtained carrier material is made into a cylindrical shape with the diameter of 2.5mm, dried at 70 ℃, and then roasted under the protection of nitrogen to obtain the catalyst carrier. With 50% Mn (NO)₃)₂·4H₂O solution and Ce (NO)₃)₃·6H₂Oto MnO₂And CeO₂The catalyst is prepared into 1000 mL solution according to the proportion of 6.0 percent and 1.5 percent of the total weight of the catalyst respectively. Supersaturation impregnation of carrier strip with Mn-Ce solution, stirring for 3 hours at 60 ℃ in thermostatic waterbath, standing for 24 hours in air, vacuum evaporating to dryness at 80 ℃ by using rotary evaporator to obtain sampleDrying the product in a drying oven at 100 ℃. Then, the catalyst was calcined at 190 ℃ for 4 hours in a muffle furnace, and the temperature was lowered to room temperature and taken out to obtain a catalyst A6. The properties of the catalyst are shown in table 1.

Example 7

Adding 50g of activated carbon powder into 200g of mixed solution of 3.3 percent of L-magnesium lactate and 6.1 percent of L-calcium aspartate by mass percent respectively, slowly stirring, and soaking for 4 hours; slowly dripping 220mL of ammonium carbonate solution with the concentration of 0.3mol/L under stirring to generate carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1000 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-magnesium oxide-calcium oxide compound. Adding the obtained compound into 200g of distilled water with the temperature of 75 ℃, introducing CO after 4h₂And (3) controlling the end point pH to be 8.0 at the temperature of 100 ℃ under the pressure of 0.40MPa, naturally cooling, filtering, drying at 50 ℃ for 6h, and roasting at 150 ℃ for 4h under the protection of nitrogen to obtain the active carbon, basic magnesium carbonate and basic calcium carbonate composite carrier material. The obtained carrier material is made into a cylindrical shape with the diameter of 3.0mm, dried at the temperature of 80 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. Zn (NO) according to its water absorption₃)₂·6H₂O and Nd (NO)₃)₃·6H₂O as ZnO and Nd₂O₃Respectively accounting for 8.0 percent and 4.5 percent of the total weight of the catalyst to prepare solutions. Soaking the carrier strip with the solution in the same volume for 2 hours, drying at 80 ℃, roasting for 4 hours at 180 ℃ in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst A7. The properties of the catalyst are shown in table 1.

TABLE 1 catalyst A1-A7 Properties

Comparative example 1

Substantially the same as in example 1 except that the 18 mass% magnesium gluconate solution was replaced with a 4.3 mass% magnesium nitrate solution, and the other conditions were changed to obtain catalyst DA 1. The properties of the catalyst are shown in table 2.

Comparative example 2

Substantially the same as example 4 except that a mixed solution of magnesium gluconate and calcium gluconate, each having a mass fraction of 8.5% and 7.2%, was replaced with a calcium chloride solution having a mass fraction of 4%, and the other conditions were not changed, thereby obtaining catalyst DA 2. The properties of the catalyst are shown in table 2.

Comparative example 3

Mechanically mixing activated carbon powder with basic magnesium carbonate and basic calcium carbonate powder according to the mass ratio of 60:30:10 to prepare the composite carrier material. The obtained carrier material is made into a cylindrical shape with the diameter of 3.0mm, dried at the temperature of 80 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. Zn (NO) according to its water absorption₃)₂·6H₂O and Nd (NO)₃)₃·6H₂O as ZnO and Nd₂O₃Respectively accounting for 8.0 percent and 4.5 percent of the total weight of the catalyst to prepare solutions. Soaking the carrier strip with the solution in the same volume for 2 hours, drying at 80 ℃, roasting for 4 hours at 180 ℃ in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst DA 3. The properties of the catalyst are shown in table 2.

Comparative example 4

Mechanically mixing activated carbon powder and basic magnesium carbonate powder according to the mass ratio of 40:60 to prepare the composite carrier material. The obtained carrier material is prepared into clover shape with the grain diameter of 2.5mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. With Mn (NO)₃)₂·4H₂O and La (NO)₃)₃·6H₂Oto MnO₂And La₂O₃The catalyst is prepared into 1000 mL solution according to the proportion of 5.0 percent and 1.5 percent of the total weight of the catalyst respectively. And supersaturating the solution to impregnate the carrier strip, stirring for 3 hours at 60 ℃ in a constant-temperature water bath, standing for 24 hours in the air, then evaporating to dryness in vacuum at 80 ℃ by using a rotary evaporator, and drying the obtained sample in a drying box at 100 ℃. Then roasting the mixture for 6 hours at 150 ℃ under the protection of nitrogen, and taking out the mixture after the temperature is reduced to room temperature to obtain the catalyst DA 4. The properties of the catalyst are shown in table 2.

TABLE 2 comparative examples 1-4 comparison of results

Evaluation test: the catalyst prepared from the catalyst support of the present invention described above and the catalyst prepared from the comparative support were evaluated.

A certain phenol-formaldehyde (1: 1) solution is used as a raw material, a catalyst is filled in a bubbling bed reactor, ozone is used as an oxidation medium, and the intermittent treatment is carried out on the catalyst, wherein the COD of the phenol-formaldehyde solution is 226 mg/L.

The treatment conditions are normal temperature and normal pressure, the dosage of the catalyst is 50g, the wastewater is 500mL, and the ozone amount is 9.7g/m³The aeration time was 30min, and the treatment results are shown in Table 3.

Table 3 comparison of catalyst evaluation results

Catalyst and process for preparing same	A1	A2	A3	A4	A5	A6	A7	DA1	DA2	DA3	DA4
												COD removal rate%	92.6	90.5	94.5	96.2	93.3	91.3	93.2	83.6	82.9	78.4	76.7
Total active metal ion concentration, mg/L	0.47	0.48	0.44	0.39	0.42	0.41	0.42	0.66	0.61	0.80	0.71

Claims

1. The catalyst comprises a composite carrier and an active metal component, wherein one or more of transition metals Fe, Cu, Mn, Ti and Zn are used as the active metal component, the composite carrier comprises active carbon and basic carbonate, and the basic carbonate is distributed on the outer surface of the active carbon, wherein the active carbon accounts for 35-90% of the total weight of the composite carrier; the basic carbonate accounts for 10-65% of the total weight of the composite carrier; the basic carbonate is basic magnesium carbonate or a mixture of the basic calcium carbonate and the basic magnesium carbonate; the preparation method of the ozone catalytic oxidation catalyst comprises the following steps:

2. The catalyst of claim 1, wherein: the active carbon accounts for 40-80% of the total weight of the composite carrier; the basic carbonate accounts for 20-60% of the total weight of the composite carrier.

3. The catalyst of claim 1, wherein: the transition metal accounts for 0.1 to 20.0 percent of the total mass of the catalyst in terms of oxidation.

4. The catalyst of claim 1, wherein: the catalyst comprises an auxiliary component, wherein the auxiliary component is a rare earth metal, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium; the rare earth metal accounts for 0.1 to 15.0 percent of the total mass of the catalyst by oxide.

5. The catalyst of claim 1, wherein: the activated carbon is powdery activated carbon, the granularity of the activated carbon is 150-300 meshes, and the specific surface area of the activated carbon is 500-3000 m²A pore volume of 0.5-1.8 cm³(ii)/g, the average pore diameter is 0.5 to 4.0nm, and the pore volume of pores having a pore diameter of 1 to 2nm accounts for 90% or more of the total pore volume.

6. The catalyst of claim 1, wherein: the specific surface area of the composite carrier is 150-1500 m²A pore volume of 0.1 to 1.2 cm/g³(ii)/g, the average pore diameter is 1-8 nm.

7. The catalyst of claim 1, wherein: the specific surface area of the catalyst is 120-1200 m²A pore volume of 0.1 to 1.8 cm/g³G, abrasion Rate<3wt% and a side pressure strength of 80 to 250N/cm.

8. A preparation method of an ozone catalytic oxidation catalyst comprises the following steps:

(5) dipping active metal and optional auxiliary agent components on the composite carrier material obtained in the step (4), and then drying and roasting to obtain a catalyst;

the soluble organic calcium salt in the step (1) is one or more of calcium gluconate, calcium acetate, calcium lactate, calcium amino acid, calcium L-aspartate and calcium L-threonate;

the soluble organic magnesium salt in the step (1) is one or more of magnesium gluconate, magnesium acetate, magnesium lactate, magnesium amino acid, magnesium L-aspartate and magnesium L-threonate.

9. The method of claim 8, wherein: the activated carbon used in the step (1) is powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m²A pore volume of 0.5-1.8 cm³(ii)/g, the average pore diameter is 0.5 to 4.0nm, and the pore volume of pores having a pore diameter of 1 to 2nm accounts for 90% or more of the total pore volume.

10. The method of claim 8, wherein: in the step (1), the soluble organic calcium salt is calcium gluconate or calcium lactate.

11. The method of claim 8, wherein: in the step (1), the soluble organic magnesium salt is magnesium gluconate or magnesium lactate.

12. The method of claim 8, wherein: in the step (1), the activated carbon and the soluble organic salt are mixed according to the ratio of C: m²⁺Mixing at a molar ratio of 4.3-84.7: 1, wherein M represents Mg or Ca and Mg.

13. The production method according to claim 8 or 12, characterized in that: in the step (1), the activated carbon and the soluble organic salt are mixed according to the ratio of C: m²⁺Mixing at a molar ratio of 10-60: 1, wherein M represents Mg or Ca and Mg.

14. The method of claim 8, wherein: in the step (2), the carbonate is one or more of ammonium carbonate, potassium carbonate and sodium carbonate, and the concentration of the carbonate solution is 0.1-1.0 mol/L.

15. The method of claim 14, wherein: in the step (2), the carbonate is ammonium carbonate.

16. The method of claim 8, wherein: the carbonate dosage in the step (2) is CO₃ ^2-：M² ⁺The molar ratio is 1-1.2: 1, wherein M represents Mg or Ca and Mg.

17. The production method according to claim 8 or 16, characterized in that: the carbonate dosage in the step (2) is CO₃ ^2-：M²⁺In a molar ratio of 1:1, wherein M represents Mg, or Ca and Mg.

18. The method of claim 8, wherein: the alkaline solution in the step (2) is an inorganic alkaline solution.

19. The method of claim 8, wherein: and (3) in the step (2), the alkaline solution is ammonia water, sodium hydroxide or potassium hydroxide.

20. The method of claim 8, wherein: and (3) introducing an alkaline solution into the material A obtained in the step (1) in the step (2), and then adjusting the pH value to 8-9.

21. The method of claim 8, wherein: the dosage of the alkaline solution in the step (2) is OH^-：M²⁺The molar ratio is 2-4: 1, wherein M represents Mg or Ca and Mg.

22. The production method according to claim 8 or 21, characterized in that: the dosage of the alkaline solution in the step (2)Is OH^-：M²⁺The molar ratio is 2-2.5: 1, wherein M represents Mg or Ca and Mg.

23. The method of claim 8, wherein: in the step (3), the drying temperature is 70-110 ℃, and the drying time is 2-6 h.

24. The production method according to claim 8 or 23, characterized in that: in the step (3), the drying temperature is 80-100 ℃, and the drying time is 3-4 h.

25. The method of claim 8, wherein: and (4) roasting in the step (3) in an inert atmosphere, wherein the inert atmosphere is one of nitrogen, argon and helium.

26. The method of claim 8, wherein: in the step (3), the roasting temperature is 500-1200 ℃, and the roasting time is 2-8 h.

27. The production method according to claim 8 or 26, characterized in that: in the step (3), the roasting temperature is 600-900 ℃, and the roasting time is 3-5 h.

28. The method of claim 8, wherein: and (4) mixing the material C with water at the temperature of 60-100 ℃.

29. The method of claim 8, wherein: in the step (4), the partial pressure of the carbon dioxide is 0.08-1.0 MPa.

30. The method of claim 8, wherein: and (4) the pH value of the reaction end point in the step (4) is 7.0-10.0.

31. The production method according to claim 8 or 30, wherein: and (4) the pH value of the reaction end point in the step (4) is 8.0-9.0.

32. The method of claim 8, wherein: the reaction temperature in the step (4) is 15-150 ℃.

33. The method of claim 8, wherein: in the step (4), the drying temperature is 40-100 ℃, and the drying time is 3-24 h.

34. The production method according to claim 8 or 33, characterized in that: in the step (4), the drying temperature is 50-60 ℃, and the drying time is 6-8 h.

35. The method of claim 8, wherein: and (4) roasting in an inert atmosphere, wherein the inert atmosphere is one of nitrogen, argon and helium.

36. The method of claim 8, wherein: in the step (4), the roasting temperature is 80-220 ℃, and the roasting time is 2-6 h.

37. The production method according to claim 8 or 36, wherein: in the step (4), the roasting temperature is 150-200 ℃, and the roasting time is 3-4 h.

38. The method of claim 8, wherein: in the step (5), the active metal component is one or more of transition metals Fe, Cu, Mn, Ti and Zn, and the transition metals account for 0.1-20.0% of the total mass of the catalyst in terms of oxides.

39. The method of claim 8, wherein: in the step (5), the auxiliary agent component is rare earth metal, the rare earth metal oxide accounts for 0.1-15.0% of the total mass of the catalyst, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium.

40. The method of claim 8, wherein: and (5) after the catalyst is impregnated, drying for 1-15 hours at 40-100 ℃, roasting for 1-10 hours at 100-220 ℃, and roasting under an inert atmosphere.